Two diastereomers of d-limonene-derived cyclic carbonates from d-limonene oxide and carbon dioxide with a tetrabutylammonium chloride catalyst

Article abstract of DOI:10.1246/bcsj.20170300

Two diastereomers of d-limonene-derived five-membered cyclic carbonates were prepared from the corresponding isomers of d-limonene oxide with CO2. Their syntheses were catalyzed by commercially available tetrabutylammonium chloride with high stereoselectivity. The reaction behavior dependent on the reaction conditions such as CO2 pressure was clarified.

Full text of DOI:10.1246/bcsj.20170300

Advance Publication Cover Page
Two Diastereomers of d-Limonene-derived Cyclic Carbonates from d-Limonene
Oxide and Carbon Dioxide with a Tetrabutylammonium Chloride Catalyst
Hiroshi Morikawa,* Masato Minamoto, Yuuta Gorou, Jun-ichi Yamaguchi,
Hisatoyo Morinaga, and Suguru Motokucho
Advance Publication on the web October 30, 2017
doi:10.1246/bcsj.20170300
©
2017 The Chemical Society of Japan

Two Diastereomers of d-Limonene-derived
Cyclic Carbonates from d-Limonene Oxide
and
Carbon
Dioxide
with
a
Tetrabutylammonium Chloride Catalyst
1
1
1
Hiroshi Morikawa,* Masato Minamoto, Yuuta Gorou,
1
2
Jun-ichi Yamaguchi, Hisatoyo Morinaga, and Suguru
3
Motokucho
1
Department of Applied Chemistry, Kanagawa Institute of Technology,
1
030, Shimo-ogino, Atsugi, Kanagawa 243-02927
2
Faculty of Education, Graduate Faculty of
Interdisciplinary Research, University of Yamanashi,
Kofu, Yamanashi 400-8510
3
Chemistry and Material Engineering Program,
Nagasaki University, Nagasaki-shi, Nagasaki
8
52-8521
Scheme 1. Synthesis of d-limonene-derived cyclic
carbonates (LM5CCs) and structures of four isomers.
E-mail: <morikawa@chem.kanagawa-it.ac.jp >
Abstract
However, synthesis and characterization of these types of
catalysts would require specific synthetic techniques and
processes as well as sufficient time. Importantly, commercially
Two diastereomers of d-limonene-derived five-membered
cyclic carbonates were prepared from the corresponding
8
isomers of d-limonene oxide with CO
catalyzed by commercially available tetrabutylammonium
chloride with high stereoselectivity. The reaction behavior
dependent on the reaction conditions such as CO
clarified.
2
. Their syntheses were
available compounds as catalysts can be instantly and directly
used, and the synthetic study with as-received catalysts is also
valuable both in academia and in industry. Therefore, we
believe that the synthesis of LM5CC by using commercially
available catalysts is of great practical importance. Additionally,
there are four kinds of diastereomers for LM5CC (Scheme 1).
Though one isomer 1A-LM5CC was successfully characterized,
another isomer 4A-LM5CC was not isolated and characterized
2
pressure was
Five-membered cyclic carbonates (5CCs) are versatile
platform compounds for functional and reactive materials,
especially for isocyanate-free synthesis of polyurethanes.
7
at all. Stereoselective synthesis of 5CCs is one of the current
1
9
research issues in this field.
Therefore, synthesis of 5CCs from the epoxides with CO
been widely studied. Today, utilization of biomass as natural
resource instead of fossil chemicals has been required. For this
2
has
Here, we report on the synthesis of LM5CCs from LO,
especially addressing the following points:
(1) Clarification of catalytic activities of commercially
available reagents such as tetrabutylammonium chloride
(TBAC) for the carbonation.
2
2
goal, fixation of CO into naturally occurring chemicals has
3
been exploited through the preparation of bio-based 5CCs.
One group of promising naturally occurring chemicals is
(2) By using TBAC, the carbonation of LO as a function
of reaction conditions is studied.
4
d-limonene as a terpene and its derivatives. It is plant waste
such as citrus peels and residues of fruit juice production.
Therefore, it does not compete with food production.
d-Limonene oxide (LO) is a substantially bio-based chemical
and is commercially available as a mixture of both cis and trans
isomers (abbreviated as c-LO and t-LO, respectively). LO is
reactive due to the epoxy moiety.
(3) Two diastereomers, 4A-LM5CC and 1A-LM5CC
(Scheme 1), obtained respectively from c-LO and t-LO, are
isolated.
1
,2
Among commercially available catalysts, TBAC was
selected as a representative catalyst. It is well known that
tetrabutylammonium halide (TBAX) is a catalyst for the
2
A LO-based 5CC obtained from LO and CO , d-limonene
1
0
11
carbonate (LM5CC), which has both a 5CC moiety and a
double bond, is a promising platform toward functional
materials because the two functional moieties are different in
their reactivity. Therefore, various kinds of synthetic processes
synthesis of 5CCs. At first, a pure isomer t-LO was reacted
with CO using 10 mol% TBAC without solvents. After 72 h at
100 °C under 3 MPa CO , the reaction mixture was evaluated
2
2
1
by H NMR analysis (SI). t-LO was quantitatively converted to
1A-LM5CC with high stereoselectivity. The reaction contained
neither byproducts nor other isomers such as 4A-LM5CC
(Scheme 1). Purification of the reaction mixture by silica gel
column chromatography to remove TBAC afforded a white
solid in a moderately good isolated yield (72%). It was revealed
5
will be possible, as is the case for LO. It is well known that an
internal epoxy moiety connected to highly substituted part of
the structure such as d-limonene is usually less reactive than a
terminal epoxy moiety. Then, transformation of the internal
6
epoxide into 5CC has been challenged. Recently, successful
1
13
synthesis of one isomer among four kinds of LM5CCs (Scheme
by H and C NMR analyses (Figures 1S, 2S in SI) that the
solid was b, 71cA-LM5CC identical to the data reported
7
1
) was reported. In the article, a catalytic system comprising
7
Al-aminotriphenolate complexes as catalysts with bis(triphenyl
phosphine)iminium chloride as a nucleophile was employed.
previously.
11
Similarly, another pure isomer c-LO was reacted with

Scheme 2. Reduction of 4A-LM5CC to 4A-LMdiol
having a set of (1R, 2S, 4R) configurations.
Figure 1. Solid state structure of 4A-LMdiol·H
2
O
2 2
CO under the same conditions (100 °C, 72 h, and 3 MPa CO ).
conditions were fixed to 10 mol% catalyst based on ct-LO at
The reaction contained no other isomers such as 1A-LM5CC.
Here, the conversion and NMR yield are defined as the
consumption of LO and the yield of LM5CC in the reaction
100 °C for 20 h under 3 MPa CO without solvents. After the
2
reaction, the reaction mixture contained 4A-LM5CC and
1
1A-LM5CC, as confirmed by comparison of H NMR spectra
1
mixture estimated by H NMR, respectively. Compared with
of the two LM5CCs. The conversion of ct-LO (sum of c-LO
and t-LO), as well as each of c-LO or t-LO, was measured from
equations in SI (Figure 7S). Similarly, the NMR yield of
4A1A-LM5CC (sum of 4A-LM5CC and 1A-LM5CC) was also
measured.
t-LO, the conversion of c-LO and NMR yield of 4A-LM5CC
were as low as 42% and 30%, respectively, even after 72 h.
Hence, the isolated yield was relatively low at 22% (Figures 3S,
4
S in SI). It was already reported that, when reacted with
nucleophiles such as primary and secondary amines, c-LO is
less reactive than t-LO because c-LO has a higher energy
As listed in Table 1, by using TBAC (run 1), the
individual conversions of c-LO and t-LO were 19% and 76%,
respectively, and 51% of ct-LO was converted in total.
Moreover, the NMR yield of 4A1A-LM5CC was 50%. The
trend for the lower reactivity of c-LO than t-LO was the same
as the aforementioned results. When the catalyst was changed
to tetrabutylammonium bromide and iodide (TBAB, TBAI),
both the conversion and NMR yield decreased. Among three
kinds of TBAX, the catalytic activity decreased in the order of
TBAC > TBAB > TBAI. This order is consistent with the
nucleophilic activity of the anionic halide ion in aprotic
transition state involving the formation of
structure. The report is in good agreement with the low
conversion and the isolated yield of the reactions of c-LO with
a boat-like
11
CO
2
in our study.
Though the isolated yield was low, 4A-LM5CC was
obtained for the first time. We also determined the
configuration of the C1 and C2 positions (Scheme 1) of the
5
CC moiety by means of reducing 4A-LM5CC with lithium
1
2-14
aluminium hydride (LAH) to the corresponding 4A-LMdiol
1
0,16
having (1R, 2S, 4R) configurations in Scheme 2. Reduction of
CC with LAH gives a corresponding diol with the same
configuration around the carbon atoms as that of the original
solvents and is the same as that reported previously.
Both
5
LiCl and LiBr (Table 9S in SI) were ineffective, presumably
because of their low solubility in ct-LO. Binary catalysts using
a mixture of LiX (X = Br or Cl, 10 mol%) and TBAC or TBAB
(10 mol%) were also applied to the carbonation reaction (Table
9S). However, the binary catalysts caused the decrease in the
NMR yield of 4A1A-LM5CC with the production of unknown
byproducts while the conversion increased.
Next, we focused on TBAC as the catalyst and studied the
effects of the reaction conditions. Starting from the typical
conditions (10 mol% TBAC based on ct-LO, 100 °C, 20 h, and
1
5
5
CC. Our X-ray analysis indicates the structure is consistent
with 4A-LMdiol of cis configuration in Figure 1 (SI for details).
Therefore, the synthesis of 4A-LM5CC was successfully
achieved, which was supported by the identification of the diol,
4
A-LMdiol.
It is elucidated that, among the four diastereomers of
LM5CCs, we achieved syntheses of 1A-LM5CC from t-LO and
A-LM5CC from c-LO with CO , stereoselectively. Other
4
2
carbonates such as 2A-LM5CC and 3A-LM5CC were not
detected. In this reaction, TBAC met the catalytic reaction
requirements. The carbonation maintained the configuration at
the C1 and C2 positions of the cyclohexane ring. A double
inversion reactions mechanism has been suggested to account
2 2
3 MPa CO ), one parameter such as CO pressure was varied.
Regarding the reaction time, the conversion of ct-LO for a
reaction time of 20 h was 51% (Table 1). Prolongation of the
time to 48 or 72 h did not sufficiently improve the conversion
of ct-LO, which was 65% or 69%, respectively. This is due to
the low conversion of c-LO within ct-LO.
7
for the maintenance.
In order to clarify the reaction behavior of LO with CO
2
in detail, we measured the conversion of LO and the NMR
yield of LM5CC as a function of the reaction conditions. Here,
not pure isomers but a mixture of as-received c-LO and t-LO
1
00
100
75
50
25
0
7
5
2
5
0
5
0
(
abbreviated as ct-LO, cis/trans = 43/57) was used as the
substrate.
First, we changed the catalysts, and commercially
available TBAX and lithium halide were selected. The reaction
a
Table 1. Reactions of ct-LO with CO2
c
c
f
conversion (%)
NMR yield (%)
b
run
catalyst
d
e
e
0
3
6
9
12
ct-LO
51
c-LO
19
t-LO
4A1A- LM5CC
1
2
3
TBAC
TBAB
TBAI
76
52
18
50
32
CO pressure (MPa)
2
36
14
22
8
7
Figure 2. Conversion of ct-LO (○), t-LO ( ), and c-LO
(□), and NMR yield of 4A1A-LM5CC (●) as a function
of CO
a
o
b
c
1
00 C, 20 h, 3 MPa CO . 10 mol% based on ct-LO. determined by
2
1
d
e
H NMR. sum of c-LO and t-LO. analyzed from the reaction
2
pressure. Reaction conditions: 10 mol% TBAC,
f
mixture of ct-LO with CO . sum of 4A-LM5CC and 1A-LM5CC
100 °C, and 20 h.
2

References
1
a) J. Datta, M. Włoch, Polym. Bull
Maisonneuve, O. Lamarzelle, E. Rix, E. Grau, H.
Cramail, Chem. Rev 2015 115, 12407. c) B. Ochiai, T.
Endo, Prog. Polym. Sci 2005 30, 183.
a) H. Büttner, L. Longwitz, J. Steinbauer, C. Wulf, T.
Werner, Top. Curr. Chem 2017 375, 50. b) T. Fujihara,
M. Inokuchi, T. Mizoe, K. Nogi, J. Terao, Y. Tsuji,
Chem. Lett 2017 46, 968. c) J. Hasegawa, R. Miyazaki,
C. Maeda, T. Ema, Chem. Rec 2016 16, 2260. d) X.-D.
Lang, L.-N. He, Chem. Rec 2016 16, 1337.
a) M. Bähr, A. Bitto, R. Mülhaupt, Green Chem
. 2016, 73, 1459. b) L.
.
,
.
,
2
.
,
.
,
.
,
.
,
3
4
5
6
7
.
2012
2012
,
,
1
1
4
4
, 1447. b) M. Bähr, R. Mülhaupt, Green Chem
, 483.
.
R. Ciriminna, M. Lomeli-Rodriguez, P. D. Carà, J. A.
Figure 3. Conversion of ct-LO (○), t-LO ( ), and c-LO
□), and NMR yield of 4A1A-LM5CC (●) as a function
of TBAC amount (mol%). Reaction conditions: 100 °C,
0 h, and 3 MPa CO
Lopez-Sanchez, M. Pagliaro, Chem. Commun. 2014
5288.
a) C. Martín, A. W. Kleij, Macromolecules 2016
,
50
,
(
1
,
49,
2
2
.
6
285. b) H. Morinaga, Y. Kiyokawa, R. Fujikawa, D.
Nagai, H. Morikawa, Polym. Bull. 2014 71, 2421.
C. J. Whiteoak, E. Martin, M. Martinez, B. J.
,
Figure 2 shows a set of conversions of LO and the NMR
yield of 4A1A-LM5CC as a function of CO pressure. Under
ambient CO pressure, the carbonation of ct-LO barely
proceeded. Once CO was pressurized, the reaction of ct-LO
Benet-Buchholz, A. W. Kleij, Adv. Synth. Catal
354, 469.
. 2012,
2
2
a) J. Martínez, J. Fernández-Baeza, L. F. Sánchez-Barba,
J. A. Casro-Osma, A. Lara-Sánchez, A. Otero,
2
smoothly proceeded. In the region examined, values of the
conversion of ct-LO were similar to those of the NMR yield.
ChemSusChem 2017
C. Martín, M. M. Belmonte, E. Martin, E. C.
Escudero-Adán, A. W. Kleij, ChemSusChem 2016
, 10, 2886. b) G. Fiorani, M. Stuck,
Before the CO
both c-LO and t-LO increased with increasing pressure. They
reached 27% and 85% under 5 MPa CO , and the NMR yield
2
pressure reached 5 MPa, the conversions of
,
9,
1
304. c) L. P. Carrodeguas, J. González-Fabra, F.
2
Castro-Gómez, C. Bo, A. W. Kleij, Chem.-Eur. J. 2015
,
of 4A1A-LM5CC reached 56%. However, when the pressure
was further increased beyond 5 MPa, the conversion decreased
slightly with increasing pressure. Next, the effect of TBAC
amount on the conversion of ct-LO and NMR yield of
21, 6115.
8
C. J. Whiteoak, N. Kielland, V. Laserna, F.
Castro-Gómez, E. Martin, E. C. Escudero-Adán, C. Bo,
A. W. Kleij, Chem.-Eur. J
C. J. Whiteoak, E. Martin, E. E.-Adán, A. W. Kleij, Adv.
Synth. Catal 2013 355, 2233.
0 S.-Y. Park, H.-Y. Park, H.-S. Lee, S.-W. Park, C.-S.
Park, D.-W. Ha, J. Polym. Sci., Part A: Polym. Chem
001 39, 1472.
1 D. Steiner, L. Ivison, C. T. Goralski, R. B. Appell, J. R.
Gojkovic, B. Singaram, Tetrahedron Asym 2002 13
359.
. 2014, 20, 2264.
9
1
4
1
A1A-LM5CC was also evaluated. As shown in Figure 3, with
mol% TBAC, the conversion was very low. The conversion
.
,
and NMR yield increased gradually with increasing TBAC
amount. The conversion of t-LO was about four times higher
than that of c-LO. With 40 mol% TBAC, t-LO reached
quantitative consumption, whereas the conversion of c-LO was
still as low as 48%.
.
2
,
1
.
,
,
2
The conversion and NMR yield depended on the
reaction temperature (Figure 10S in SI). At 60 °C and 80 °C,
the conversion of ct-LO was 15% and 24%, respectively. It is
obvious that the increase of temperature enhanced the
conversion and NMR yield. When the temperature was raised
to 100 °C or 120 °C, the conversion increased to 51% or 71%,
respectively. It increased to 75% at 140 °C; however, unknown
by-products in a NMR yield of ~ca. 5% were detected. From
these results in Figures 2, 3, and 10S, it became clear that
LM5CCs can be obtained with only TBAC by choosing the
reaction conditions.
12 a) B. Hao, M. J. Gunaratna, M. Zhang, S. Weerasekara,
S. N. Seiwald, V. T. Nguyen, A. Meier, D. H. Hua, J.
Am. Chem. Soc
R. Manjunatha, P. Srinivas, B. K. Bettadaiah, J. Chem.
Sci. 2014 126, 875.
. 2016, 138, 16839. b) S. C. S. Kumar, J.
,
1
3 Ref. 12b) was cited in ref. 12a). However, the reaction
mechanism of d-limonene-1,2-diol in ref.
1
2b) indicates clearly the formation of an
isomer having not (1
R
,
,
2
2S,
S
,
4
4
R
R
)
)
configurations but (1
S
configurations. Indeed,1 the chemical
3
shifts, especially in the C NMR, in ref.
In conclusion, LO with CO
2
was reacted to give
12 are close to those for the (1
isomer in ref. 14.
S, 2S, 4R)
d-limonene-derived 5CCs (LM5CCs). Among the four kinds of
diastereomers of LM5CCs, we achieved the individual
synthesis of 4A-LM5CC from cis-LO and 1A-LM5CC from
trans-LO. The syntheses can be made highly stereoselective
simply by commercially available TBAC. Moreover, we
studied the relationship between the reaction conditions and the
conversion of LO and NMR yield of LM5CCs. We believe that
1
4 a) S. Águila, R. Vazquez-Duhalt, R. Tinoco, M. Rivera,
G. Pecchi, J. B. Alderete, Green Chem 2008 10, 647. b)
Z. Wang, Y.-T. Cui, Z.-B. Xu, J. Qu, J. Org. Chem
008 73, 2270.
.
,
.
2
,
1
1
5 P. A. Wender, N. Buschmann, N. B. Cardin, L. R. Jones,
C. Kan, J.-M. Kee, J. A. Kowalski, K. E. Longcore, Nat.
Chem. 2011, 3, 615.
6 N. Kihara, N. Hara, T. Endo, J. Org. Chem. 1993, 58,
this synthetic study will help to develop
a bio-based
polyurethane industrial process starting from LM5CC, as well
as the synthesis of limonene-derived bioactive compounds.
6198.
Supporting Information
Supplemental
data,
experimental
procedures,
characterization data.

Graphical Abstract
Title>
<
Two Diastereomers of d-Limonene-derived Cyclic Carbonates from d-Limonene Oxide and Carbon Dioxide with a
Tetrabutylammonium Chloride Catalyst
<
Authors' names>
Hiroshi Morikawa, Masato Minamoto, Yuuta Gorou, Jun-ichi Yamaguchi, Hisatoyo Morinaga, and Suguru Motokucho
<
Summary>
Two diastereomers of d-limonene-derived five-membered cyclic carbonates were prepared from the corresponding isomers of
d-limonene oxide with CO . Their syntheses were catalyzed by commercially available tetrabutylammonium chloride with high
stereoselectivity. The reaction behavior dependent on the reaction conditions such as CO pressure was clarified.
2
2
<
Diagram>